河南省清凉寺窑址出土富铁釉瓷的无损分析研究
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摘要
富铁釉瓷在中国古陶瓷史上具有重要地位,综合利用光学相干层析成像技术(OCT)、光学显微镜(OM)、激光拉曼光谱技术(LRS)和X射线荧光光谱分析技术(XRF)对河南省宝丰清凉寺窑址出土宋金时期富铁釉瓷样品进行无损分析研究,获取了富铁釉瓷的釉层结构、釉面析晶的物相信息及胎釉化学成分等信息,探讨了釉层断面OCT灰度图像特征与其显微结构之间的关系以及富铁釉瓷的烧制工艺。结果表明,酱釉瓷和柿叶红釉瓷表面及黑釉红斑区存在富铁析晶层,黑釉瓷釉层表面未发现富铁析晶层的存在。酱釉瓷釉层富铁析晶层中铁的氧化物以ε-Fe_2O_3晶体为主,而柿叶红釉层则主要是α-Fe_2O_3晶体,黑釉红斑层同时存在ε-Fe_2O_3,α-Fe_2O_3晶体以及磁铁矿。上述差异形成的原因与釉层化学成和烧制工艺存在联系。釉层中高含量碱土金属氧化物及氧化铁区域更容易析出氧化铁晶体。黑釉瓷烧成气氛以还原气氛为主,而酱釉瓷和柿叶红釉瓷则倾向于氧化烧成气氛,且柿叶红釉瓷的烧成温度高于酱釉瓷。该研究将OCT,OM,LRS与XRF相结合,有助于加强对富铁釉瓷的整体认知,为富铁釉瓷的断源断代提供更为丰富的线索。
Iron rich porcelain has an important position in the history of Chinese ancient ceramics.Optical Coherence Tomography(OCT)combined with Optical microscope(OM),laser Raman spectroscopy(LRS)and X-ray fluorescence spectroscopy(XRF)is used to analyze the Iron rich porcelain dated to Jin and Yuan dynasty and excavated from Qingliangsi site in Baofeng County,Henan Province.The structure of iron rich glaze,the phase information of crystal and chemical composition of glaze and body are obtained,and the relationship between the OCT image and microstructure of section of glaze layer and the firing process of iron rich porcelain are discussed.The results show thatthe surfaces of sauce glazed porcelain,persimmon leaf red glazed porcelain and the red spot area of black glaze existiron-rich crystal layer,but from the surface of black glaze we have not found the existence of iron-rich crystal layer.ε-Fe_2O_3 is the main iron oxide in iron-rich crystal layer of sauce glaze layer,whileα-Fe_2O_3 is the main one in persimmon leaf red glaze layer,and thered spot area of black porcelain has all ofε-Fe_2O_3,α-Fe_2O_3 and magnetite.The reasons for the above differences are related to thechemical composition of glaze and the firing process.It is easier for the area of high content alkaline-earth metallic oxide andiron oxide in glaze layer to precipitate iron oxide crystal.And the firing atmosphere of black-glazed porcelain is reducing condition,while sauce glazed porcelain and persimmon leaf red glazed porcelain are inclined to oxidizing condition.Moreover,the firing temperature of persimmon leaf red glazed porcelain is higher than that of sauce glazed porcelain.This study combining OCTwith OM,LRS and XRF has great significance for enhancing the overall understanding of iron rich porcelain and providing more abundant clues for confirming the production sites and periods of iron rich porcelain.
Iron rich porcelain has an important position in the history of Chinese ancient ceramics.Optical Coherence Tomography(OCT)combined with Optical microscope(OM),laser Raman spectroscopy(LRS)and X-ray fluorescence spectroscopy(XRF)is used to analyze the Iron rich porcelain dated to Jin and Yuan dynasty and excavated from Qingliangsi site in Baofeng County,Henan Province.The structure of iron rich glaze,the phase information of crystal and chemical composition of glaze and body are obtained,and the relationship between the OCT image and microstructure of section of glaze layer and the firing process of iron rich porcelain are discussed.The results show thatthe surfaces of sauce glazed porcelain,persimmon leaf red glazed porcelain and the red spot area of black glaze existiron-rich crystal layer,but from the surface of black glaze we have not found the existence of iron-rich crystal layer.ε-Fe_2O_3 is the main iron oxide in iron-rich crystal layer of sauce glaze layer,whileα-Fe_2O_3 is the main one in persimmon leaf red glaze layer,and thered spot area of black porcelain has all ofε-Fe_2O_3,α-Fe_2O_3 and magnetite.The reasons for the above differences are related to thechemical composition of glaze and the firing process.It is easier for the area of high content alkaline-earth metallic oxide andiron oxide in glaze layer to precipitate iron oxide crystal.And the firing atmosphere of black-glazed porcelain is reducing condition,while sauce glazed porcelain and persimmon leaf red glazed porcelain are inclined to oxidizing condition.Moreover,the firing temperature of persimmon leaf red glazed porcelain is higher than that of sauce glazed porcelain.This study combining OCTwith OM,LRS and XRF has great significance for enhancing the overall understanding of iron rich porcelain and providing more abundant clues for confirming the production sites and periods of iron rich porcelain.
引文
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[17] ZHANG Yi(张义).Bulletin of The Chinese Ceramic Society(硅酸盐通报),2008,(3):503.